Solid Electrolytic Capacitor Assembly for Use in a Humid Atmosphere

ABSTRACT

A capacitor assembly that is capable of exhibiting good properties under humid conditions. The ability to perform under such conditions is due in part to the use of an intrinsically conductive polymer in the solid electrolyte that contains repeating units having the following formula (I): 
     
       
         
         
             
             
         
       
     
     wherein,
         R is (CH 2 ) a —O—(CH 2 ) b ;   a is from 0 to 10;   b is from 1 to 18;   Z is an anion; and   X is a cation.       

     Due to its unique structure, the polymer is not highly sensitive to moisture. Consequently, the resulting capacitor assembly may exhibit excellent electrical properties even when exposed to high humidity levels.

BACKGROUND OF THE INVENTION

Solid electrolytic capacitors (e.g., tantalum capacitors) are typicallymade by pressing a metal powder (e.g., tantalum) around a metal leadwire, sintering the pressed part, anodizing the sintered anode, andthereafter applying a solid electrolyte. Intrinsically conductivepolymers are often employed as the solid electrolyte due to theiradvantageous low equivalent series resistance (“ESR”) and“non-burning/non-ignition” failure mode. For example, such electrolytescan be formed through in situ chemical polymerization of a3,4-dioxythiophene monomer (“EDOT”) in the presence of a catalyst anddopant. For example, such electrolytes can be formed through in situchemical polymerization of a 3,4-dioxythiophene monomer (“EDOT”) in thepresence of a catalyst and dopant. However, conventional capacitors thatemploy in situ polymerized polymers tend to have a relatively highleakage current (“DCL”) and fail at high voltages, such as experiencedduring a fast switch on or operational current spike. In an attempt toovercome these issues, dispersions have also been employed that areformed from a complex of poly(3,4-ethylenedioxythiophene) andpoly(styrene sulfonic acid (“PEDOT:PSS”). While the PEDOT:PSSdispersions can result in some improved properties, the polymer tends tooxidize when exposed to humid environments (e.g., 85% relativehumidity), thus decreasing the thermal stability of the capacitorassembly.

As such, a need currently exists for a capacitor that has improvedperformance in high humidity environments.

SUMMARY OF THE INVENTION

In accordance with one embodiment of the present invention, a capacitorassembly is disclosed that is in contact with an atmosphere having arelative humidity of about 40% or more. The capacitor assembly comprisesa capacitor element that includes an anode that contains a dielectricformed on a sintered porous body and a solid electrolyte overlying theanode. The solid electrolyte includes an intrinsically conductivepolymer containing repeating units having the following formula (I):

wherein,

R is (CH₂)_(a)—O—(CH₂)_(b);

a is from 0 to 10;

b is from 1 to 18;

Z is an anion; and

X is a cation.

Other features and aspects of the present invention are set forth ingreater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

A full and enabling disclosure of the present invention, including thebest mode thereof, directed to one of ordinary skill in the art, is setforth more particularly in the remainder of the specification, whichmakes reference to the appended figures in which:

FIG. 1 is a cross-sectional view of one embodiment of a capacitorassembly of the assembly of the present invention;

FIG. 2 is a cross-sectional view of another embodiment of a capacitorassembly of the assembly of the present invention;

FIG. 3 is a cross-sectional view of yet another embodiment of acapacitor assembly of the assembly of the present invention; and

FIG. 4 is a top view of still another embodiment of a capacitor assemblyof the assembly of the present invention.

Repeat use of references characters in the present specification anddrawings is intended to represent same or analogous features or elementsof the invention.

DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS

It is to be understood by one of ordinary skill in the art that thepresent discussion is a description of exemplary embodiments only, andis not intended as limiting the broader aspects of the presentinvention, which broader aspects are embodied in the exemplaryconstruction.

Generally speaking, the present invention is directed to a capacitorassembly that is capable of exhibiting good properties under humidconditions. The ability to perform under such conditions is due in partto the use of an intrinsically conductive polymer in the solidelectrolyte that contains repeating units having the following formula(I):

wherein,

R is (CH₂)_(a)—O—(CH₂)_(b);

a is from 0 to 10, in some embodiments from 0 to 6, and in someembodiments, from 1 to 4 (e.g., 1);

b is from 1 to 18, in some embodiments from 1 to 10, and in someembodiments, from 2 to 6 (e.g., 3, 4, or 5);

Z is an anion, such as SO₃ ⁻, C(O)O⁻, BF₄ ⁻, CF₃SO₃ ⁻, SbF₆ ⁻,N(SO₂CF₃)₂ ⁻, C₄H₃O₄ ⁻, ClO₄ ⁻, etc.;

X is a cation, such as hydrogen, an alkali metal (e.g., lithium, sodium,rubidium, cesium or potassium), ammonium, etc.

Due to its unique structure, the polymer is not highly sensitive tomoisture. Consequently, the resulting capacitor assembly may exhibitexcellent electrical properties even when exposed to high humiditylevels, such as when placed into contact with an atmosphere having arelative humidity of about 40% or more, in some embodiments about 45% ormore, in some embodiments about 50% or more, and in some embodiments,about 70% or more (e.g., about 85% to 100%). Relative humidity may, forinstance, be determined in accordance with ASTM E337-02, Method A(2007). The humid atmosphere may be part of the internal atmosphere ofthe capacitor assembly itself, or it may be an external atmosphere towhich the capacitor assembly is exposed during storage and/or use. Thecapacitor may also exhibit a relatively low equivalence seriesresistance (“ESR”), such as about 200 mohms, in some embodiments lessthan about 150 mohms, in some embodiments from about 0.01 to about 125mohms, and in some embodiments, from about 0.1 to about 100 mohms,measured at an operating frequency of 100 kHz. The capacitor assemblymay also exhibit a high percentage of its wet capacitance, which enablesit to have only a small capacitance loss and/or fluctuation in thepresence of atmosphere humidity. This performance characteristic isquantified by the “wet-to-dry capacitance percentage”, which isdetermined by the equation:

Wet-to-Dry Capacitance=(Dry Capacitance/Wet Capacitance)×100

The capacitor assembly may exhibit a wet-to-dry capacitance percentageof about 50% or more, in some embodiments about 60% or more, in someembodiments about 70% or more, and in some embodiments, from about 80%to 100%. The dry capacitance may be about 30 nanoFarads per squarecentimeter (“nF/cm²”) or more, in some embodiments about 100 nF/cm² ormore, in some embodiments from about 200 to about 3,000 nF/cm², and insome embodiments, from about 400 to about 2,000 nF/cm², measured at afrequency of 120 Hz. Such ESR and capacitance values may even bemaintained for a substantial amount of time and at high temperatures.For example, the values may be maintained for about 100 hours or more,in some embodiments from about 300 hours to about 3000 hours, and insome embodiments, from about 400 hours to about 2500 hours (e.g., 500hours, 600 hours, 700 hours, 800 hours, 900 hours, 1000 hours, 1100hours, 1200 hours, or 2000 hours) at temperatures ranging from 50° C. to250° C., and, in some embodiments from 70° C. to 200° C., and in someembodiments, from 80° C. to about 150° C. (e.g., 85° C.), and at a highhumidity level. In one embodiment, for instance, the values may bemaintained for 1000 hours at a temperature of 85° C.

Various embodiments of the present invention will now be described inmore detail.

I. Capacitor Element

A. Anode Body

The capacitor element includes an anode that contains a dielectricformed on a sintered porous body. The porous anode body may be formedfrom a powder that contains a valve metal (i.e., metal that is capableof oxidation) or valve metal-based compound, such as tantalum, niobium,aluminum, hafnium, titanium, alloys thereof, oxides thereof, nitridesthereof, and so forth. The powder is typically formed from a reductionprocess in which a tantalum salt (e.g., potassium fluotantalate(K₂TaF₇), sodium fluotantalate (Na₂TaF₇), tantalum pentachloride(TaCl₅), etc.) is reacted with a reducing agent. The reducing agent maybe provided in the form of a liquid, gas (e.g., hydrogen), or solid,such as a metal (e.g., sodium), metal alloy, or metal salt. In oneembodiment, for instance, a tantalum salt (e.g., TaCl₅) may be heated ata temperature of from about 900° C. to about 2,000° C., in someembodiments from about 1,000° C. to about 1,800° C., and in someembodiments, from about 1,100° C. to about 1,600° C., to form a vaporthat can be reduced in the presence of a gaseous reducing agent (e.g.,hydrogen). Additional details of such a reduction reaction may bedescribed in WO 2014/199480 to Maeshima, et al. After the reduction, theproduct may be cooled, crushed, and washed to form a powder.

The specific charge of the powder typically varies from about 2,000 toabout 800,000 microFarads*Volts per gram (“μF*V/g”) depending on thedesired application. For instance, in certain embodiments, a high chargepowder may be employed that has a specific charge of from about 100,000to about 800,000 μF*V/g, in some embodiments from about 120,000 to about700,000 μF*V/g, and in some embodiments, from about 150,000 to about600,000 μF*V/g. In other embodiments, a low charge powder may beemployed that has a specific charge of from about 2,000 to about 100,000μF*V/g, in some embodiments from about 5,000 to about 80,000 μF*V/g, andin some embodiments, from about 10,000 to about 70,000 μF*V/g. As isknown in the art, the specific charge may be determined by multiplyingcapacitance by the anodizing voltage employed, and then dividing thisproduct by the weight of the anodized electrode body.

The powder may be a free-flowing, finely divided powder that containsprimary particles. The primary particles of the powder generally have amedian size (D50) of from about 5 to about 500 nanometers, in someembodiments from about 10 to about 400 nanometers, and in someembodiments, from about 20 to about 250 nanometers, such as determinedusing a laser particle size distribution analyzer made by BECKMANCOULTER Corporation (e.g., LS-230), optionally after subjecting theparticles to an ultrasonic wave vibration of 70 seconds. The primaryparticles typically have a three-dimensional granular shape (e.g.,nodular or angular). Such particles typically have a relatively low“aspect ratio”, which is the average diameter or width of the particlesdivided by the average thickness (“D/T”). For example, the aspect ratioof the particles may be about 4 or less, in some embodiments about 3 orless, and in some embodiments, from about 1 to about 2. In addition toprimary particles, the powder may also contain other types of particles,such as secondary particles formed by aggregating (or agglomerating) theprimary particles. Such secondary particles may have a median size (D50)of from about 1 to about 500 micrometers, and in some embodiments, fromabout 10 to about 250 micrometers.

Agglomeration of the particles may occur by heating the particles and/orthrough the use of a binder. For example, agglomeration may occur at atemperature of from about 0° C. to about 40° C., in some embodimentsfrom about 5° C. to about 35° C., and in some embodiments, from about15° C. to about 30° C. Suitable binders may likewise include, forinstance, poly(vinyl butyral); poly(vinyl acetate); poly(vinyl alcohol);poly(vinyl pyrollidone); cellulosic polymers, such ascarboxymethylcellulose, methyl cellulose, ethyl cellulose, hydroxyethylcellulose, and methylhydroxyethyl cellulose; atactic polypropylene,polyethylene; polyethylene glycol (e.g., Carbowax from Dow ChemicalCo.); polystyrene, poly(butadiene/styrene); polyamides, polyimides, andpolyacrylamides, high molecular weight polyethers; copolymers ofethylene oxide and propylene oxide; fluoropolymers, such aspolytetrafluoroethylene, polyvinylidene fluoride, and fluoro-olefincopolymers; acrylic polymers, such as sodium polyacrylate, poly(loweralkyl acrylates), poly(lower alkyl methacrylates) and copolymers oflower alkyl acrylates and methacrylates; and fatty acids and waxes, suchas stearic and other soapy fatty acids, vegetable wax, microwaxes(purified paraffins), etc.

The resulting powder may be compacted to form a pellet using anyconventional powder press device. For example, a press mold may beemployed that is a single station compaction press containing a die andone or multiple punches. Alternatively, anvil-type compaction pressmolds may be used that use only a die and single lower punch. Singlestation compaction press molds are available in several basic types,such as cam, toggle/knuckle and eccentric/crank presses with varyingcapabilities, such as single action, double action, floating die,movable platen, opposed ram, screw, impact, hot pressing, coining orsizing. The powder may be compacted around an anode lead, which may bein the form of a wire, sheet, etc. The lead may extend in a longitudinaldirection from the anode body and may be formed from any electricallyconductive material, such as tantalum, niobium, aluminum, hafnium,titanium, etc., as well as electrically conductive oxides and/ornitrides of thereof. Connection of the lead may also be accomplishedusing other known techniques, such as by welding the lead to the body orembedding it within the anode body during formation (e.g., prior tocompaction and/or sintering).

Any binder may be removed after pressing by heating the pellet undervacuum at a certain temperature (e.g., from about 150° C. to about 500°C.) for several minutes. Alternatively, the binder may also be removedby contacting the pellet with an aqueous solution, such as described inU.S. Pat. No. 6,197,252 to Bishop, et al. Thereafter, the pellet issintered to form a porous, integral mass. The pellet is typicallysintered at a temperature of from about 700° C. to about 1600° C., insome embodiments from about 800° C. to about 1500° C., and in someembodiments, from about 900° C. to about 1200° C., for a time of fromabout 5 minutes to about 100 minutes, and in some embodiments, fromabout 8 minutes to about 15 minutes. This may occur in one or moresteps. If desired, sintering may occur in an atmosphere that limits thetransfer of oxygen atoms to the anode. For example, sintering may occurin a reducing atmosphere, such as in a vacuum, inert gas, hydrogen, etc.The reducing atmosphere may be at a pressure of from about 10 Torr toabout 2000 Torr, in some embodiments from about 100 Torr to about 1000Torr, and in some embodiments, from about 100 Torr to about 930 Torr.Mixtures of hydrogen and other gases (e.g., argon or nitrogen) may alsobe employed.

B. Dielectric

The anode is also coated with a dielectric. The dielectric may be formedby anodically oxidizing (“anodizing”) the sintered anode so that adielectric layer is formed over and/or within the anode. For example, atantalum (Ta) anode may be anodized to tantalum pentoxide (Ta₂O₅).Typically, anodization is performed by initially applying a solution tothe anode, such as by dipping anode into the electrolyte. A solvent isgenerally employed, such as water (e.g., deionized water). To enhanceionic conductivity, a compound may be employed that is capable ofdissociating in the solvent to form ions. Examples of such compoundsinclude, for instance, acids, such as described below with respect tothe electrolyte. For example, an acid (e.g., phosphoric acid) mayconstitute from about 0.01 wt. % to about 5 wt. %, in some embodimentsfrom about 0.05 wt. % to about 0.8 wt. %, and in some embodiments, fromabout 0.1 wt. % to about 0.5 wt. % of the anodizing solution. Ifdesired, blends of acids may also be employed.

A current is passed through the anodizing solution to form thedielectric layer. The value of the formation voltage manages thethickness of the dielectric layer. For example, the power supply may beinitially set up at a galvanostatic mode until the required voltage isreached. Thereafter, the power supply may be switched to apotentiostatic mode to ensure that the desired dielectric thickness isformed over the entire surface of the anode. Of course, other knownmethods may also be employed, such as pulse or step potentiostaticmethods. The voltage at which anodic oxidation occurs typically rangesfrom about 4 to about 250 V, and in some embodiments, from about 5 toabout 200 V, and in some embodiments, from about 10 to about 150 V.During oxidation, the anodizing solution can be kept at an elevatedtemperature, such as about 30° C. or more, in some embodiments fromabout 40° C. to about 200° C., and in some embodiments, from about 50°C. to about 100° C. Anodic oxidation can also be done at ambienttemperature or lower. The resulting dielectric layer may be formed on asurface of the anode and within its pores.

Although not required, in certain embodiments, the dielectric layer maypossess a differential thickness throughout the anode in that itpossesses a first portion that overlies an external surface of the anodeand a second portion that overlies an interior surface of the anode. Insuch embodiments, the first portion is selectively formed so that itsthickness is greater than that of the second portion. It should beunderstood, however, that the thickness of the dielectric layer need notbe uniform within a particular region. Certain portions of thedielectric layer adjacent to the external surface may, for example,actually be thinner than certain portions of the layer at the interiorsurface, and vice versa. Nevertheless, the dielectric layer may beformed such that at least a portion of the layer at the external surfacehas a greater thickness than at least a portion at the interior surface.Although the exact difference in these thicknesses may vary depending onthe particular application, the ratio of the thickness of the firstportion to the thickness of the second portion is typically from about1.2 to about 40, in some embodiments from about 1.5 to about 25, and insome embodiments, from about 2 to about 20.

To form a dielectric layer having a differential thickness, amulti-stage process is generally employed. In each stage of the process,the sintered anode is anodically oxidized (“anodized”) to form adielectric layer (e.g., tantalum pentoxide). During the first stage ofanodization, a relatively small forming voltage is typically employed toensure that the desired dielectric thickness is achieved for the innerregion, such as forming voltages ranging from about 1 to about 90 volts,in some embodiments from about 2 to about 50 volts, and in someembodiments, from about 5 to about 20 volts. Thereafter, the sinteredbody may then be anodically oxidized in a second stage of the process toincrease the thickness of the dielectric to the desired level. This isgenerally accomplished by anodizing in an electrolyte at a highervoltage than employed during the first stage, such as at formingvoltages ranging from about 50 to about 350 volts, in some embodimentsfrom about 60 to about 300 volts, and in some embodiments, from about 70to about 200 volts. During the first and/or second stages, theelectrolyte may be kept at a temperature within the range of from about15° C. to about 95° C., in some embodiments from about 20° C. to about90° C., and in some embodiments, from about 25° C. to about 85° C.

The electrolytes employed during the first and second stages of theanodization process may be the same or different. Typically, however, itis desired to employ different solutions to help better facilitate theattainment of a higher thickness at the outer portions of the dielectriclayer. For example, it may be desired that the electrolyte employed inthe second stage has a lower ionic conductivity than the electrolyteemployed in the first stage to prevent a significant amount of oxidefilm from forming on the internal surface of anode. In this regard, theelectrolyte employed during the first stage may contain an acidiccompound, such as hydrochloric acid, nitric acid, sulfuric acid,phosphoric acid, polyphosphoric acid, boric acid, boronic acid, etc.Such an electrolyte may have an electrical conductivity of from about0.1 to about 100 mS/cm, in some embodiments from about 0.2 to about 20mS/cm, and in some embodiments, from about 1 to about 10 mS/cm,determined at a temperature of 25° C. The electrolyte employed duringthe second stage typically contains a salt of a weak acid so that thehydronium ion concentration increases in the pores as a result of chargepassage therein. Ion transport or diffusion is such that the weak acidanion moves into the pores as necessary to balance the electricalcharges. As a result, the concentration of the principal conductingspecies (hydronium ion) is reduced in the establishment of equilibriumbetween the hydronium ion, acid anion, and undissociated acid, thusforms a poorer-conducting species. The reduction in the concentration ofthe conducting species results in a relatively high voltage drop in theelectrolyte, which hinders further anodization in the interior while athicker oxide layer, is being built up on the outside to a higherformation voltage in the region of continued high conductivity. Suitableweak acid salts may include, for instance, ammonium or alkali metalsalts (e.g., sodium, potassium, etc.) of boric acid, boronic acid,acetic acid, oxalic acid, lactic acid, adipic acid, etc. Particularlysuitable salts include sodium tetraborate and ammonium pentaborate. Suchelectrolytes typically have an electrical conductivity of from about 0.1to about 20 mS/cm, in some embodiments from about 0.5 to about 10 mS/cm,and in some embodiments, from about 1 to about 5 mS/cm, determined at atemperature of 25° C.

If desired, each stage of anodization may be repeated for one or morecycles to achieve the desired dielectric thickness. Furthermore, theanode may also be rinsed or washed with another solvent (e.g., water)after the first and/or second stages to remove the electrolyte.

C. Solid Electrolyte

A solid electrolyte overlies the dielectric and generally functions asthe cathode for the capacitor assembly. Typically, the total thicknessof the solid electrolyte is from about 1 to about 50 μm, and in someembodiments, from about 5 to about 20 μm. As indicated above, the solidelectrolyte contains an intrinsically conductive polymer havingrepeating units of the following formula (I):

wherein,

R is (CH₂)_(a)—O—(CH₂)_(b);

a is from 0 to 10, in some embodiments from 0 to 6, and in someembodiments, from 1 to 4 (e.g., 1);

b is from 1 to 18, in some embodiments from 1 to 10, and in someembodiments, from 2 to 6 (e.g., 2, 3, 4, or 5);

Z is an anion, such as SO₃ ⁻, C(O)O⁻, BF₄ ⁻, CF₃SO₃ ⁻, N(SO₂CF₃)₂ ⁻,C₄H₃O₄ ⁻, ClO₄ ⁻, etc.;

X is a cation, such as hydrogen, an alkali metal (e.g., lithium, sodium,rubidium, cesium or potassium), ammonium, etc.

In one particular embodiment, Z in formula (I) is a sulfonate ion suchthat the intrinsically conductive polymer contains repeating units ofthe following formula (II):

wherein, R and X are defined above. In formula (I) or (II), a ispreferably 1 and b is preferably 3 or 4. Likewise, X is preferablysodium or potassium.

If desired, the polymer may be a copolymer that contains other types ofrepeating units. In such embodiments, the repeating units of formula (I)typically constitute about 50 mol. % or more, in some embodiments fromabout 75 mol. % to about 99 mol. %, and in some embodiments, from about85 mol. % to about 95 mol. % of the total amount of repeating units inthe copolymer. Of course, the polymer may also be a homopolymer to theextent that it contains 100 mol. % of the repeating units of formula(I). Specific examples of such homopolymers includepoly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butane-sulphonicacid, salt) andpoly(4-(2,3-dihydrothieno-[3,4-b][I,4]dioxin-2-ylmethoxy)-I-propanesulphonicacid, salt).

The intrinsically conductive polymer may be formed through a variety oftechniques as would be understood by those skilled in the art. In oneparticular embodiment, for example, a 3,4-ethylenedioxythiophene saltmay be polymerized in the presence of an oxidative catalyst. Derivativesof these monomers may also be employed that are, for example, dimers ortrimers of the above compounds. The derivatives may be made up ofidentical or different monomer units and used in pure form and in amixture with one another and/or with the monomers. Oxidized or reducedforms of these precursors may also be employed. The oxidative catalystmay be a transition metal salt, such as a salt of an inorganic ororganic acid that contain ammonium, sodium, gold, iron(III), copper(II),chromium(VI), cerium(IV), manganese(IV), manganese(VII), orruthenium(III) cations. Particularly suitable transition metal saltsinclude halides (e.g., FeCl₃ or HAuCl₄); salts of other inorganic acids(e.g., Fe(ClO₄)₃, Fe₂(SO₄)₃, (NH₄)₂S₂O₈, or Na₃Mo₁₂PO₄₀); and salts oforganic acids and inorganic acids comprising organic radicals. Examplesof salts of inorganic acids with organic radicals include, for instance,iron(III) salts of sulfuric acid monoesters of C₁ to C₂₀ alkanols (e.g.,iron(III) salt of lauryl sulfate). Likewise, examples of salts oforganic acids include, for instance, iron(III) salts of C₁ to C₂₀ alkanesulfonic acids (e.g., methane, ethane, propane, butane, or dodecanesulfonic acid); iron (III) salts of aliphatic perfluorosulfonic acids(e.g., trifluoromethane sulfonic acid, perfluorobutane sulfonic acid, orperfluorooctane sulfonic acid); iron (III) salts of aliphatic C₁ to C₂₀carboxylic acids (e.g., 2-ethylhexylcarboxylic acid); iron (III) saltsof aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acid orperfluorooctane acid); iron (III) salts of aromatic sulfonic acidsoptionally substituted by C₁ to C₂₀ alkyl groups (e.g., benzene sulfonicacid, o-toluene sulfonic acid, p-toluene sulfonic acid, ordodecylbenzene sulfonic acid); iron (III) salts of cycloalkane sulfonicacids (e.g., camphor sulfonic acid); and so forth. Mixtures of theseabove-mentioned salts may also be used.

Oxidative polymerization generally occurs in the presence of one or moresolvents. Suitable solvents may include, for instance, water, glycols(e.g., ethylene glycol, propylene glycol, butylene glycol, triethyleneglycol, hexylene glycol, polyethylene glycols, ethoxydiglycol,dipropyleneglycol, etc.); glycol ethers (e.g., methyl glycol ether,ethyl glycol ether, isopropyl glycol ether, etc.); alcohols (e.g.,methanol, ethanol, n-propanol, iso-propanol, and butanol); ketones(e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone); esters(e.g., ethyl acetate, butyl acetate, diethylene glycol ether acetate,methoxypropyl acetate, ethylene carbonate, propylene carbonate, etc.);amides (e.g., dimethylformamide, dimethylacetamide,dimethylcaprylic/capric fatty acid amide and N-alkylpyrrolidones);sulfoxides or sulfones (e.g., dimethyl sulfoxide (DMSO) and sulfolane);phenolic compounds (e.g., toluene, xylene, etc.), and so forth. Water isa particularly suitable solvent for the reaction. The temperature atwhich the reaction occurs typically varies from about −20° C. to about140° C., and in some embodiments, from about 20° C. to about 100° C.Upon completion of the reaction, known filtration techniques may beemployed to remove any salt impurities.

Regardless of how it is formed, the polymer is considered“intrinsically” conductive to the extent that it has a positive chargelocated on the main chain that is at least partially compensated byanions covalently bound to the polymer. The polymer may, for example,have a relatively high specific conductivity, in the dry state, of about1 Siemen per centimeter (“S/cm”) or more, in some embodiments about 10S/cm or more, in some embodiments about 20 S/cm or more, and in someembodiments, from about 50 to about 500 S/cm. As a result of itsintrinsic conductivity, the solid electrolyte does not require theaddition of conventional dopants, such as polystyrene sulfonic acid. Infact, the solid electrolyte may be substantially free of such dopants.Nevertheless, it should be understood that dopants may be employed incertain embodiments of the present invention. When utilized, however,dopants are typically present in the solid electrolyte in an amount ofabout 5 wt. % or less, in some embodiments about 2 wt. % or less, and insome embodiments, about 1 wt. % or less.

The polymer is also generally highly soluble in water, which enables itto be more easily and effectively applied to the anode. The solublepolymer is also able to more readily impregnate the small pores formedby the high specific charge powder, so that the resulting solidelectrolyte has a “film-like” configuration and coats at least a portionof the anode in a substantially uniform manner. This improves thequality of the resulting oxide as well as its surface coverage, andthereby enhances the electrical properties of the capacitor assembly.

i. Inner Layers

The solid electrolyte is generally formed from one or more “inner”conductive polymer layers. The term “inner” in this context refers toone or more layers formed from the same material and that overly thedielectric, whether directly or via another layer (e.g., adhesivelayer). The inner layer(s), for example, typically contain anintrinsically conductive polymer such as described above. Through theuse of such a polymer, the present inventors have discovered that thecapacitor element can exhibit better performance under humid conditions.In one particular embodiment, the inner layer(s) are generally free ofextrinsically conductive polymers and thus formed primarily fromintrinsically conductive polymers. More particularly, intrinsicallyconductive polymers may constitute about 50 wt. % or more, in someembodiments about 70 wt. % or more, and in some embodiments, about 90wt. % or more (e.g., 100 wt. %) of the inner layer(s). One or multipleinner layers may be employed. For example, the solid electrolytetypically contains from 2 to 30, in some embodiments from 4 to 20, andin some embodiments, from about 5 to 15 inner layers (e.g., 10 layers).

The inner layer(s) may be applied in the form of a solution containing asolvent. The concentration of the polymer may vary depending on thedesired viscosity of and the particular manner in which the layer is tobe applied to the anode. Typically, however, the polymer constitutesfrom about 0.1 to about 10 wt. %, in some embodiments from about 0.4 toabout 5 wt. %, and in some embodiments, from about 0.5 to about 4 wt. %of the solution. Solvent(s) may likewise constitute from about 90 wt. %to about 99.9 wt. %, in some embodiments from about 95 wt % to about99.6 wt. %, and in some embodiments, from about 96 wt. % to about 99.5wt. % of the solution. While other solvents may certainly be employed,it is generally desired that water is the primary solvent such that thesolution is considered an “aqueous” solution. In most embodiments, forexample, water constitutes at least about 50 wt. %, in some embodimentsat least about 75 wt. %, and in some embodiments, from about 90 wt. % to100 wt. % of the solvent(s) employed. When employed, a solution may beapplied to the anode using any known technique, such as dipping, casting(e.g., curtain coating, spin coating, etc.), printing (e.g., gravureprinting, offset printing, screen printing, etc.), and so forth. Theresulting conductive polymer layer may be dried and/or washed after itis applied to the anode.

ii. Outer Layers

The solid electrolyte may contain only “inner layers” so that it isessentially formed from the same material, i.e., intrinsicallyconductive polymers. Nevertheless, in other embodiments, the solidelectrolyte may also contain one or more optional “outer” conductivepolymer layers that are formed from a different material than the innerlayer(s) and overly the inner layer(s). For example, the outer layer(s)may be formed from a dispersion of extrinsically conductive polymerparticles. In one particular embodiment, the outer layer(s) are formedprimarily from such extrinsically conductive polymer particles in thatthey constitute about 50 wt. % or more, in some embodiments about 70 wt.% or more, and in some embodiments, about 90 wt. % or more (e.g., 100wt. %) of a respective outer layer. One or multiple outer layers may beemployed. For example, the solid electrolyte may contain from 2 to 30,in some embodiments from 4 to 20, and in some embodiments, from about 5to 15 outer layers, each of which may optionally be formed from adispersion of the extrinsically conductive polymer particles.

When employed, the extrinsically conductive polymer may, for instance,have repeating units of the following formula (III):

wherein,

R₇ is a linear or branched, C₁ to C₁₈ alkyl radical (e.g., methyl,ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl,n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.); C₅ to C₁₂cycloalkyl radical (e.g., cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, etc.); C₆ to C₁₄ aryl radical (e.g.,phenyl, naphthyl, etc.); C₇ to C₁₈ aralkyl radical (e.g., benzyl, o-,m-, p-tolyl, 2,3-, 2,4-, 2,5-, 2-6, 3-4-, 3,5-xylyl, mesityl, etc.); C₁to C₄ hydroxyalkyl radical, or hydroxyl radical; and

q is an integer from 0 to 8, in some embodiments, from 0 to 2, and inone embodiment, 0. In one particular embodiment, “q” is 0 and thepolymer is poly(3,4-ethylenedioxythiophene). One commercially suitableexample of a monomer suitable for forming such a polymer is3,4-ethylenedioxthiophene, which is available from Heraeus under thedesignation Clevios™ M.

The polymers of formula (III) are generally considered to be“extrinsically” conductive to the extent that they require the presenceof a separate counterion that is not covalently bound to the polymer.The counterion may be a monomeric or polymeric anion that counteractsthe charge of the conductive polymer. Polymeric anions can, for example,be anions of polymeric carboxylic acids (e.g., polyacrylic acids,polymethacrylic acid, polymaleic acids, etc.); polymeric sulfonic acids(e.g., polystyrene sulfonic acids (“PSS”), polyvinyl sulfonic acids,etc.); and so forth. The acids may also be copolymers, such ascopolymers of vinyl carboxylic and vinyl sulfonic acids with otherpolymerizable monomers, such as acrylic acid esters and styrene.Likewise, suitable monomeric anions include, for example, anions of C₁to C₂₀ alkane sulfonic acids (e.g., dodecane sulfonic acid); aliphaticperfluorosulfonic acids (e.g., trifluoromethane sulfonic acid,perfluorobutane sulfonic acid or perfluorooctane sulfonic acid);aliphatic C₁ to C₂₀ carboxylic acids (e.g., 2-ethyl-hexylcarboxylicacid); aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acidor perfluorooctanoic acid); aromatic sulfonic acids optionallysubstituted by C₁ to C₂₀ alkyl groups (e.g., benzene sulfonic acid,o-toluene sulfonic acid, p-toluene sulfonic acid or dodecylbenzenesulfonic acid); cycloalkane sulfonic acids (e.g., camphor sulfonic acidor tetrafluoroborates, hexafluorophosphates, perchlorates,hexafluoroantimonates, hexafluoroarsenates or hexachloroantimonates);and so forth. Particularly suitable counteranions are polymeric anions,such as a polymeric carboxylic or sulfonic acid (e.g., polystyrenesulfonic acid (“PSS”)). The molecular weight of such polymeric anionstypically ranges from about 1,000 to about 2,000,000, and in someembodiments, from about 2,000 to about 500,000.

The extrinsically conductive particles typically have an average size(e.g., diameter) of from about 1 to about 150 nanometers, in someembodiments from about 2 to about 50 nanometers, and in someembodiments, from about 5 to about 40 nanometers. The diameter of theparticles may be determined using known techniques, such as byultracentrifuge, laser diffraction, etc. The shape of the particles maylikewise vary. In one particular embodiment, for instance, the particlesare spherical in shape. However, it should be understood that othershapes are also contemplated by the present invention, such as plates,rods, discs, bars, tubes, irregular shapes, etc. The concentration ofthe particles in the dispersion may vary depending on the desiredviscosity of the dispersion and the particular manner in which thedispersion is to be applied to the capacitor element. Typically,however, the particles constitute from about 0.1 to about 10 wt. %, insome embodiments from about 0.4 to about 5 wt. %, and in someembodiments, from about 0.5 to about 4 wt. % of the dispersion.

The dispersion may also contain one or more binders to further enhancethe adhesive nature of the polymeric layer and also increase thestability of the particles within the dispersion. The binders may beorganic in nature, such as polyvinyl alcohols, polyvinyl pyrrolidones,polyvinyl chlorides, polyvinyl acetates, polyvinyl butyrates,polyacrylic acid esters, polyacrylic acid amides, polymethacrylic acidesters, polymethacrylic acid amides, polyacrylonitriles, styrene/acrylicacid ester, vinyl acetate/acrylic acid ester and ethylene/vinyl acetatecopolymers, polybutadienes, polyisoprenes, polystyrenes, polyethers,polyesters, polycarbonates, polyurethanes, polyamides, polyimides,polysulfones, melamine formaldehyde resins, epoxide resins, siliconeresins or celluloses. Crosslinking agents may also be employed toenhance the adhesion capacity of the binders. Such crosslinking agentsmay include, for instance, melamine compounds, masked isocyanates orfunctional silanes, such as 3-glycidoxypropyltrialkoxysilane,tetraethoxysilane and tetraethoxysilane hydrolysate or crosslinkablepolymers, such as polyurethanes, polyacrylates or polyolefins, andsubsequent crosslinking.

Dispersion agents may also be employed to facilitate the ability toapply the layer to the anode. Suitable dispersion agents includesolvents, such as aliphatic alcohols (e.g., methanol, ethanol,i-propanol and butanol), aliphatic ketones (e.g., acetone and methylethyl ketones), aliphatic carboxylic acid esters (e.g., ethyl acetateand butyl acetate), aromatic hydrocarbons (e.g., toluene and xylene),aliphatic hydrocarbons (e.g., hexane, heptane and cyclohexane),chlorinated hydrocarbons (e.g., dichloromethane and dichloroethane),aliphatic nitriles (e.g., acetonitrile), aliphatic sulfoxides andsulfones (e.g., dimethyl sulfoxide and sulfolane), aliphatic carboxylicacid amides (e.g., methylacetamide, dimethylacetamide anddimethylformamide), aliphatic and araliphatic ethers (e.g., diethyletherand anisole), water, and mixtures of any of the foregoing solvents. Aparticularly suitable dispersion agent is water.

In addition to those mentioned above, still other ingredients may alsobe used in the dispersion. For example, conventional fillers may be usedthat have a size of from about 10 nanometers to about 100 micrometers,in some embodiments from about 50 nanometers to about 50 micrometers,and in some embodiments, from about 100 nanometers to about 30micrometers. Examples of such fillers include calcium carbonate,silicates, silica, calcium or barium sulfate, aluminum hydroxide, glassfibers or bulbs, wood flour, cellulose powder carbon black, electricallyconductive polymers, etc. The fillers may be introduced into thedispersion in powder form, but may also be present in another form, suchas fibers.

Surface-active substances may also be employed in the dispersion, suchas ionic or non-ionic surfactants. Furthermore, adhesives may beemployed, such as organofunctional silanes or their hydrolysates, forexample 3-glycidoxypropyltrialkoxysilane, 3-aminopropyl-triethoxysilane,3-mercaptopropyl-trimethoxysilane, 3-metacryloxypropyltrimethoxysilane,vinyltrimethoxysilane or octyltriethoxysilane. The dispersion may alsocontain additives that increase conductivity, such as ethergroup-containing compounds (e.g., tetrahydrofuran), lactonegroup-containing compounds (e.g., y-butyrolactone or y-valerolactone),amide or lactam group-containing compounds (e.g., caprolactam,N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide,N,N-dimethylformamide (DMF), N-methylformamide, N-methylformanilide,N-methylpyrrolidone (NMP), N-octylpyrrolidone, or pyrrolidone), sulfonesand sulfoxides (e.g., sulfolane (tetramethylenesulfone) ordimethylsulfoxide (DMSO)), sugar or sugar derivatives (e.g., saccharose,glucose, fructose, or lactose), sugar alcohols (e.g., sorbitol ormannitol), furan derivatives (e.g., 2-furancarboxylic acid or3-furancarboxylic acid), an alcohols (e.g., ethylene glycol, glycerol,di- or triethylene glycol).

The dispersion may be applied using a variety of known techniques, suchas by spin coating, impregnation, pouring, dropwise application,injection, spraying, doctor blading, brushing, printing (e.g., ink-jet,screen, or pad printing), or dipping. The viscosity of the dispersion istypically from about 0.1 to about 100,000 mPas (measured at a shear rateof 100 s⁻¹), in some embodiments from about 1 to about 10,000 mPas, insome embodiments from about 10 to about 1,500 mPas, and in someembodiments, from about 100 to about 1000 mPas.

If desired, a hydroxyl-functional nonionic polymer may also be employedin the outer layer(s) of the solid electrolyte. The term“hydroxy-functional” generally means that the compound contains at leastone hydroxyl functional group or is capable of possessing such afunctional group in the presence of a solvent. Without intending to belimited by theory, it is believed that the use of a hydroxy-functionalpolymer with a certain molecular weight can minimize the likelihood ofchemical decomposition at high voltages. For instance, the molecularweight of the hydroxy-functional polymer may be from about 100 to 10,000grams per mole, in some embodiments from about 200 to 2,000, in someembodiments from about 300 to about 1,200, and in some embodiments, fromabout 400 to about 800.

Any of a variety of hydroxy-functional nonionic polymers may generallybe employed for this purpose. In one embodiment, for example, thehydroxy-functional polymer is a polyalkylene ether. Polyalkylene ethersmay include polyalkylene glycols (e.g., polyethylene glycols,polypropylene glycols polytetramethylene glycols, polyepichlorohydrins,etc.), polyoxetanes, polyphenylene ethers, polyether ketones, and soforth. Polyalkylene ethers are typically predominantly linear, nonionicpolymers with terminal hydroxy groups. Particularly suitable arepolyethylene glycols, polypropylene glycols and polytetramethyleneglycols (polytetrahydrofurans), which are produced by polyaddition ofethylene oxide, propylene oxide or tetrahydrofuran onto water. Thepolyalkylene ethers may be prepared by polycondensation reactions fromdiols or polyols. The diol component may be selected, in particular,from saturated or unsaturated, branched or unbranched, aliphaticdihydroxy compounds containing 5 to 36 carbon atoms or aromaticdihydroxy compounds, such as, for example, pentane-1,5-diol,hexane-1,6-diol, neopentyl glycol, bis-(hydroxymethyl)-cyclohexanes,bisphenol A, dimer diols, hydrogenated dimer diols or even mixtures ofthe diols mentioned. In addition, polyhydric alcohols may also be usedin the polymerization reaction, including for example glycerol, di- andpolyglycerol, trimethylolpropane, pentaerythritol or sorbitol.

In addition to those noted above, other hydroxy-functional nonionicpolymers may also be employed in the present invention. Some examples ofsuch polymers include, for instance, ethoxylated alkylphenols;ethoxylated or propoxylated C₆-C₂₄ fatty alcohols; polyoxyethyleneglycol alkyl ethers having the general formula:CH₃—(CH₂)₁₀₋₁₆—(O—C₂H₄)₁₋₂₅—OH (e.g., octamethylene glycol monododecylether and pentamethylene glycol monododecyl ether); polyoxypropyleneglycol alkyl ethers having the general formula:CH₃—(CH₂)₁₀₋₁₆—(O—C₃H₆)₁₋₂₅—OH; polyoxyethylene glycol octylphenolethers having the following general formula:C₈H₁₇—(C₆H₄)—(O—C₂H₄)₁₋₂₅—OH (e.g., Triton™ X-100); polyoxyethyleneglycol alkylphenol ethers having the following general formula:C₉H₁₉—(C₆H₄)—(O—C₂H₄)₁₋₂₅—OH (e.g., nonoxynol-9); polyoxyethylene glycolesters of C₈-C₂₄ fatty acids, such as polyoxyethylene glycol sorbitanalkyl esters (e.g., polyoxyethylene (20) sorbitan monolaurate,polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20)sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, PEG-20methyl glucose distearate, PEG-20 methyl glucose sesquistearate, PEG-80castor oil, and PEG-20 castor oil, PEG-3 castor oil, PEG 600 dioleate,and PEG 400 dioleate) and polyoxyethylene glycerol alkyl esters (e.g.,polyoxyethylene-23 glycerol laurate and polyoxyethylene-20 glycerolstearate); polyoxyethylene glycol ethers of C₈-C₂₄ fatty acids (e.g.,polyoxyethylene-10 cetyl ether, polyoxyethylene-10 stearyl ether,polyoxyethylene-20 cetyl ether, polyoxyethylene-10 oleyl ether,polyoxyethylene-20 oleyl ether, polyoxyethylene-20 isohexadecyl ether,polyoxyethylene-15 tridecyl ether, and polyoxyethylene-6 tridecylether); block copolymers of polyethylene glycol and polypropylene glycol(e.g., Poloxamers); and so forth, as well as mixtures thereof.

The hydroxy-functional nonionic polymer may be incorporated into theouter layers in a variety of different ways. In certain embodiments, forinstance, the nonionic polymer may simply be incorporated into thedispersion of extrinsically conductive polymers. In such embodiments,the concentration of the nonionic polymer in the layer may be from about1 wt. % to about 50 wt. %, in some embodiments from about 5 wt. % toabout 40 wt. %, and in some embodiments, from about 10 wt. % to about 30wt. %. In other embodiments, however, the nonionic polymer may beapplied after the initial outer layer(s) are formed. In suchembodiments, the technique used to apply the nonionic polymer may vary.For example, the nonionic polymer may be applied in the form of a liquidsolution using various methods, such as immersion, dipping, pouring,dripping, injection, spraying, spreading, painting or printing, forexample, inkjet, screen printing or tampon printing. Solvents known tothe person skilled in the art can be employed in the solution, such aswater, alcohols, or a mixture thereof. The concentration of the nonionicpolymer in such a solution typically ranges from about 5 wt. % to about95 wt. %, in some embodiments from about 10 wt. % to about 70 wt. %, andin some embodiments, from about 15 wt. % to about 50 wt. % of thesolution. If desired, such solutions may be generally free of conductivepolymers. For example, conductive polymers may constitute about 2 wt. %or less, in some embodiments about 1 wt. % or less, and in someembodiments, about 0.5 wt. % or less of the solution.

D. External Polymer Coating

Although not required, an external polymer coating may also be appliedto the anode that overlies the solid electrolyte. The external polymercoating generally contains one or more layers formed from a dispersionof extrinsically conductive polymer particles, such as described above.The external coating may be able to further penetrate into the edgeregion of the capacitor body to increase the adhesion to the dielectricand result in a more mechanically robust part, which may reduceequivalent series resistance and leakage current. Because it isgenerally intended to improve the degree of edge coverage rather toimpregnate the interior of the anode body, the particles used in theexternal coating typically have a larger size than those employed in anyoptional dispersions of the solid electrolyte. For example, the ratio ofthe average size of the particles employed in the external polymercoating to the average size of the particles employed in any dispersionof the solid electrolyte is typically from about 1.5 to about 30, insome embodiments from about 2 to about 20, and in some embodiments, fromabout 5 to about 15. For example, the particles employed in thedispersion of the external coating may have an average size of fromabout 50 to about 500 nanometers, in some embodiments from about 80 toabout 250 nanometers, and in some embodiments, from about 100 to about200 nanometers.

If desired, a crosslinking agent may also be employed in the externalpolymer coating to enhance the degree of adhesion to the solidelectrolyte. Typically, the crosslinking agent is applied prior toapplication of the dispersion used in the external coating. Suitablecrosslinking agents are described, for instance, in U.S. PatentPublication No. 2007/0064376 to Merker, et al, and include, forinstance, amines (e.g., diamines, triamines, oligomer amines,polyamines, etc.); polyvalent metal cations, such as salts or compoundsof Mg, Al, Ca, Fe, Cr, Mn, Ba, Ti, Co, Ni, Cu, Ru, Ce or Zn, phosphoniumcompounds, sulfonium compounds, etc. Particularly suitable examplesinclude, for instance, 1,4-diaminocyclohexane,1,4-bis(amino-methyl)cyclohexane, ethylenediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine,1,10-decanediamine, 1,12-dodecanediamine, N,N-dimethylethylenediamine,N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetramethyl-1,4-butanediamine, etc., as well as mixturesthereof.

The crosslinking agent is typically applied from a solution ordispersion whose pH is from 1 to 10, in some embodiments from 2 to 7, insome embodiments, from 3 to 6, as determined at 25° C. Acidic compoundsmay be employed to help achieve the desired pH level. Examples ofsolvents or dispersants for the crosslinking agent include water ororganic solvents, such as alcohols, ketones, carboxylic esters, etc. Thecrosslinking agent may be applied to the capacitor body by any knownprocess, such as spin-coating, impregnation, casting, dropwiseapplication, spray application, vapor deposition, sputtering,sublimation, knife-coating, painting or printing, for example inkjet,screen or pad printing. Once applied, the crosslinking agent may bedried prior to application of the polymer dispersion. This process maythen be repeated until the desired thickness is achieved. For example,the total thickness of the entire external polymer coating, includingthe crosslinking agent and dispersion layers, may range from about 1 toabout 50 μm, in some embodiments from about 2 to about 40 μm, and insome embodiments, from about 5 to about 20 μm.

E. Other Components

If desired, the capacitor element may also contain other layers as isknown in the art. For example, a protective coating may optionally beformed between the dielectric and solid electrolyte, such as one made ofa relatively insulative resinous material (natural or synthetic). Suchmaterials may have a specific resistivity of greater than about 10 Ω·cm,in some embodiments greater than about 100, in some embodiments greaterthan about 1,000 Ω·cm, in some embodiments greater than about 1×10⁵Ω·cm, and in some embodiments, greater than about 1×10¹⁰ Ω·cm. Someresinous materials that may be utilized in the present inventioninclude, but are not limited to, polyurethane, polystyrene, esters ofunsaturated or saturated fatty acids (e.g., glycerides), and so forth.For instance, suitable esters of fatty acids include, but are notlimited to, esters of lauric acid, myristic acid, palmitic acid, stearicacid, eleostearic acid, oleic acid, linoleic acid, linolenic acid,aleuritic acid, shellolic acid, and so forth. These esters of fattyacids have been found particularly useful when used in relativelycomplex combinations to form a “drying oil”, which allows the resultingfilm to rapidly polymerize into a stable layer. Such drying oils mayinclude mono-, di-, and/or tri-glycerides, which have a glycerolbackbone with one, two, and three, respectively, fatty acyl residuesthat are esterified. For instance, some suitable drying oils that may beused include, but are not limited to, olive oil, linseed oil, castoroil, tung oil, soybean oil, and shellac. These and other protectivecoating materials are described in more detail U.S. Pat. No. 6,674,635to Fife, et al., which is incorporated herein in its entirety byreference thereto for all purposes.

If desired, the part may also be applied with a carbon layer (e.g.,graphite) and silver layer, respectively. The silver coating may, forinstance, act as a solderable conductor, contact layer, and/or chargecollector for the capacitor and the carbon coating may limit contact ofthe silver coating with the solid electrolyte. Such coatings may coversome or all of the solid electrolyte.

II. Terminations

Once formed, the capacitor element may be provided with terminations,particularly when employed in surface mounting applications. Forexample, the capacitor assembly may contain an anode termination towhich an anode lead of the capacitor element is electrically connectedand a cathode termination to which the cathode of the capacitor elementis electrically connected. Any conductive material may be employed toform the terminations, such as a conductive metal (e.g., copper, nickel,silver, nickel, zinc, tin, palladium, lead, copper, aluminum,molybdenum, titanium, iron, zirconium, magnesium, and alloys thereof).Particularly suitable conductive metals include, for instance, copper,copper alloys (e.g., copper-zirconium, copper-magnesium, copper-zinc, orcopper-iron), nickel, and nickel alloys (e.g., nickel-iron). Thethickness of the terminations is generally selected to minimize thethickness of the capacitor. For instance, the thickness of theterminations may range from about 0.05 to about 1 millimeter, in someembodiments from about 0.05 to about 0.5 millimeters, and from about0.07 to about 0.2 millimeters. One exemplary conductive material is acopper-iron alloy metal plate available from Wieland (Germany). Ifdesired, the surface of the terminations may be electroplated withnickel, silver, gold, tin, etc. as is known in the art to ensure thatthe final part is mountable to the circuit board. In one particularembodiment, both surfaces of the terminations are plated with nickel andsilver flashes, respectively, while the mounting surface is also platedwith a tin solder layer.

The terminations may be connected to the capacitor element using anytechnique known in the art. In one embodiment, for example, a lead framemay be provided that defines the cathode termination and anodetermination. To attach the electrolytic capacitor element to the leadframe, a conductive adhesive may initially be applied to a surface ofthe cathode termination. The conductive adhesive may include, forinstance, conductive metal particles contained with a resin composition.The metal particles may be silver, copper, gold, platinum, nickel, zinc,bismuth, etc. The resin composition may include a thermoset resin (e.g.,epoxy resin), curing agent (e.g., acid anhydride), and coupling agent(e.g., silane coupling agents). Suitable conductive adhesives may bedescribed in U.S. Patent Application Publication No. 2006/0038304 toOsako, et al. Any of a variety of techniques may be used to apply theconductive adhesive to the cathode termination. Printing techniques, forinstance, may be employed due to their practical and cost-savingbenefits. The anode lead may also be electrically connected to the anodetermination using any technique known in the art, such as mechanicalwelding, laser welding, conductive adhesives, etc. Upon electricallyconnecting the anode lead to the anode termination, the conductiveadhesive may then be cured to ensure that the electrolytic capacitorelement is adequately adhered to the cathode termination.

III. Housing

Due to the ability of the capacitor assembly to exhibit good electricalperformance in humid environments, it is not necessary for the capacitorelement to be hermetically sealed within a housing. Nevertheless, incertain embodiments, it may be desired to hermetically seal thecapacitor element within a housing. In one embodiment, for example, thecapacitor element may be hermetically sealed within a housing in thepresence of a gaseous atmosphere that contains an inert gas, therebyfurther limiting the amount of moisture supplied to the solidelectrolyte of the capacitor element.

The capacitor element may be sealed within a housing in various ways. Incertain embodiments, for instance, the capacitor element may be enclosedwithin a case, which may then be filled with a resinous material, suchas a thermoset resin (e.g., epoxy resin) that can be cured to form ahardened housing. Examples of such resins include, for instance, epoxyresins, polyimide resins, melamine resins, urea-formaldehyde resins,polyurethane resins, phenolic resins, polyester resins, etc. Epoxyresins are also particularly suitable. Still other additives may also beemployed, such as photoinitiators, viscosity modifiers, suspensionaiding agents, pigments, stress reducing agents, non-conductive fillers,stabilizers, etc. For example, the non-conductive fillers may includeinorganic oxide particles, such as silica, alumina, zirconia, magnesiumoxide, iron oxide, copper oxide, zeolites, silicates, clays (e.g.,smectite clay), etc., as well as composites (e.g., alumina-coated silicaparticles) and mixtures thereof. Regardless, the resinous material maysurround and encapsulate the capacitor element so that at least aportion of the anode and cathode terminations are exposed for mountingonto a circuit board. When encapsulated in this manner, the capacitorelement and resinous material form an integral capacitor assembly.

Of course, in alternative embodiments, it may be desirable to enclosethe capacitor element within a housing that remains separate anddistinct. In this manner, the atmosphere of the housing can possess acertain degree of moisture such that it is considered a humidatmosphere. For example, the relative humidity of the atmosphere may beabout 40% or more, in some embodiments about 45% or more, and in someembodiments, from about 50% to about 95% (e.g., about 50%). Inalternative embodiments, however, the atmosphere may be relatively dryso that it has a relative humidity of less than about 40%, in someembodiments about 30% or less, in some embodiments about 10% or less,and in some embodiments, from about 0.001 to about 5%. For example, theatmosphere may be gaseous and contain at least one inert gas, such asnitrogen, helium, argon, xenon, neon, krypton, radon, and so forth, aswell as mixtures thereof. Typically, inert gases constitute the majorityof the atmosphere within the housing, such as from about 50 wt. % to 100wt. %, in some embodiments from about 75 wt. % to 100 wt. %, and in someembodiments, from about 90 wt. % to about 99 wt. % of the atmosphere. Ifdesired, a relatively small amount of non-inert gases may also beemployed, such as carbon dioxide, oxygen, water vapor, etc. In suchcases, however, the non-inert gases typically constitute 15 wt. % orless, in some embodiments 10 wt. % or less, in some embodiments about 5wt. % or less, in some embodiments about 1 wt. % or less, and in someembodiments, from about 0.01 wt. % to about 1 wt. % of the atmospherewithin the housing.

Any of a variety of different materials may be used to form the housing,such as metals, plastics, ceramics, and so forth. In one embodiment, forexample, the housing includes one or more layers of a metal, such astantalum, niobium, aluminum, nickel, hafnium, titanium, copper, silver,steel (e.g., stainless), alloys thereof (e.g., electrically conductiveoxides), composites thereof (e.g., metal coated with electricallyconductive oxide), and so forth. In another embodiment, the housing mayinclude one or more layers of a ceramic material, such as aluminumnitride, aluminum oxide, silicon oxide, magnesium oxide, calcium oxide,glass, etc., as well as combinations thereof.

The housing may have any desired shape, such as cylindrical, D-shaped,rectangular, triangular, prismatic, etc. Referring to FIG. 1, forexample, one embodiment of a capacitor assembly 100 is shown thatcontains a housing 122 and a capacitor element 120. In this particularembodiment, the housing 122 is generally rectangular. Typically, thehousing and the capacitor element have the same or similar shape so thatthe capacitor element can be readily accommodated within the interiorcavity. In the illustrated embodiment, for example, both the capacitorelement 120 and the housing 122 have a generally rectangular shape.

If desired, the capacitor assembly of the present invention may exhibita relatively high volumetric efficiency. To facilitate such highefficiency, the capacitor element typically occupies a substantialportion of the volume of an interior cavity of the housing. For example,the capacitor element may occupy about 30 vol. % or more, in someembodiments about 50 vol. % or more, in some embodiments about 60 vol. %or more, in some embodiments about 70 vol. % or more, in someembodiments from about 80 vol. % to about 98 vol. %, and in someembodiments, from about 85 vol. % to 97 vol. % of the interior cavity ofthe housing. To this end, the difference between the dimensions of thecapacitor element and those of the interior cavity defined by thehousing are typically relatively small.

Referring to FIG. 1, for example, the capacitor element 120 may have alength (excluding the length of the anode lead 6) that is relativelysimilar to the length of an interior cavity 126 defined by the housing122. For example, the ratio of the length of the anode to the length ofthe interior cavity ranges from about 0.40 to 1.00, in some embodimentsfrom about 0.50 to about 0.99, in some embodiments from about 0.60 toabout 0.99, and in some embodiments, from about 0.70 to about 0.98. Thecapacitor element 120 may have a length of from about 5 to about 10millimeters, and the interior cavity 126 may have a length of from about6 to about 15 millimeters. Similarly, the ratio of the height of thecapacitor element 120 (in the −z direction) to the height of theinterior cavity 126 may range from about 0.40 to 1.00, in someembodiments from about 0.50 to about 0.99, in some embodiments fromabout 0.60 to about 0.99, and in some 0.25 embodiments, from about 0.70to about 0.98. The ratio of the width of the capacitor element 120 (inthe −x direction) to the width of the interior cavity 126 may also rangefrom about 0.50 to 1.00, in some embodiments from about 0.60 to about0.99, in some embodiments from about 0.70 to about 0.99, in someembodiments from about 0.80 to about 0.98, and in some embodiments, fromabout 0.85 to about 0.95. For example, the width of the capacitorelement 120 may be from about 2 to about 7 millimeters and the width ofthe interior cavity 126 may be from about 3 to about 10 millimeters, andthe height of the capacitor element 120 may be from about 0.5 to about 2millimeters and the width of the interior cavity 126 may be from about0.7 to about 6 millimeters.

Although by no means required, the capacitor element may be attached tothe housing in such a manner that an anode termination and cathodetermination are formed external to the housing for subsequentintegration into a circuit. The particular configuration of theterminations may depend on the intended application. In one embodiment,for example, the capacitor assembly may be formed so that it is surfacemountable, and yet still mechanically robust. For example, the anodelead may be electrically connected to external, surface mountable anodeand cathode terminations (e.g., pads, sheets, plates, frames, etc.).Such terminations may extend through the housing to connect with thecapacitor. The thickness or height of the terminations is generallyselected to minimize the thickness of the capacitor assembly. Forinstance, the thickness of the terminations may range from about 0.05 toabout 1 millimeter, in some embodiments from about 0.05 to about 0.5millimeters, and from about 0.1 to about 0.2 millimeters. If desired,the surface of the terminations may be electroplated with nickel,silver, gold, tin, etc. as is known in the art to ensure that the finalpart is mountable to the circuit board. In one particular embodiment,the termination(s) are deposited with nickel and silver flashes,respectively, and the mounting surface is also plated with a tin solderlayer. In another embodiment, the termination(s) are deposited with thinouter metal layers (e.g., gold) onto a base metal layer (e.g., copperalloy) to further increase conductivity.

In certain embodiments, connective members may be employed within theinterior cavity of the housing to facilitate connection to theterminations in a mechanically stable manner. For example, referringagain to FIG. 1, the capacitor assembly 100 may include a connectionmember 162 that is formed from a first portion 167 and a second portion165. The connection member 162 may be formed from conductive materialssimilar to the external terminations. The first portion 167 and secondportion 165 may be integral or separate pieces that are connectedtogether, either directly or via an additional conductive element (e.g.,metal). In the illustrated embodiment, the second portion 165 isprovided in a plane that is generally parallel to a lateral direction inwhich the lead 6 extends (e.g., −y direction). The first portion 167 is“upstanding” in the sense that it is provided in a plane that isgenerally perpendicular the lateral direction in which the lead 6extends. In this manner, the first portion 167 can limit movement of thelead 6 in the horizontal direction to enhance surface contact andmechanical stability during use. If desired, an insulative material 7(e.g., Teflon™ washer) may be employed around the lead 6.

The first portion 167 may possess a mounting region (not shown) that isconnected to the anode lead 6. The region may have a “U-shape” forfurther enhancing surface contact and mechanical stability of the lead6. Connection of the region to the lead 6 may be accomplished using anyof a variety of known techniques, such as welding, laser welding,conductive adhesives, etc. In one particular embodiment, for example,the region is laser welded to the anode lead 6. Regardless of thetechnique chosen, however, the first portion 167 can hold the anode lead6 in substantial horizontal alignment to further enhance the dimensionalstability of the capacitor assembly 100.

Referring again to FIG. 1, one embodiment of the present invention isshown in which the connective member 162 and capacitor element 120 areconnected to the housing 122 through anode and cathode terminations 127and 129, respectively. More specifically, the housing 122 of thisembodiment includes an outer wall 123 and two opposing sidewalls 124between which a cavity 126 is formed that includes the capacitor element120. The outer wall 123 and sidewalls 124 may be formed from one or morelayers of a metal, plastic, or ceramic material such as described above.In this particular embodiment, the anode termination 127 contains afirst region 127 a that is positioned within the housing 122 andelectrically connected to the connection member 162 and a second region127 b that is positioned external to the housing 122 and provides amounting surface 201. Likewise, the cathode termination 129 contains afirst region 129 a that is positioned within the housing 122 andelectrically connected to the solid electrolyte of the capacitor element120 and a second region 129 b that is positioned external to the housing122 and provides a mounting surface 203. It should be understood thatthe entire portion of such regions need not be positioned within orexternal to the housing.

In the illustrated embodiment, a conductive trace 127 c extends in theouter wall 123 of the housing to connect the first region 127 a andsecond region 127 b. Similarly, a conductive trace 129 c extends in theouter wall 123 of the housing to connect the first region 127 a andsecond region 127 b. The conductive traces and/or regions of theterminations may be separate or integral. In addition to extendingthrough the outer wall of the housing, the traces may also be positionedat other locations, such as external to the outer wall. Of course, thepresent invention is by no means limited to the use of conductive tracesfor forming the desired terminations.

Regardless of the particular configuration employed, connection of theterminations 127 and 129 to the capacitor element 120 may be made usingany known technique, such as welding, laser welding, conductiveadhesives, etc. In one particular embodiment, for example, a conductiveadhesive 131 is used to connect the second portion 165 of the connectionmember 162 to the anode termination 127. Likewise, a conductive adhesive133 is used to connect the cathode of the capacitor element 120 to thecathode termination 129.

Optionally, a polymeric restraint may also be disposed in contact withone or more surfaces of the capacitor element, such as the rear surface,front surface, upper surface, lower surface, side surface(s), or anycombination thereof. The polymeric restraint can reduce the likelihoodof delamination by the capacitor element from the housing. In thisregard, the polymeric restraint may possesses a certain degree ofstrength that allows it to retain the capacitor element in a relativelyfixed positioned even when it is subjected to vibrational forces, yet isnot so strong that it cracks. For example, the restraint may possess atensile strength of from about 1 to about 150 Megapascals (“MPa”), insome embodiments from about 2 to about 100 MPa, in some embodiments fromabout 10 to about 80 MPa, and in some embodiments, from about 20 toabout 70 MPa, measured at a temperature of about 25° C. It is normallydesired that the restraint is not electrically conductive. Referringagain to FIG. 1, for instance, one embodiment is shown in which a singlepolymeric restraint 197 is disposed in contact with an upper surface 181and rear surface 177 of the capacitor element 120. While a singlerestraint is shown in FIG. 1, it should be understood that separaterestraints may be employed to accomplish the same function. In fact,more generally, any number of polymeric restraints may be employed tocontact any desired surface of the capacitor element. When multiplerestraints are employed, they may be in contact with each other orremain physically separated. For example, in one embodiment, a secondpolymeric restraint (not shown) may be employed that contacts the uppersurface 181 and front surface 179 of the capacitor element 120. Thefirst polymeric restraint 197 and the second polymeric restraint (notshown) may or may not be in contact with each other. In yet anotherembodiment, a polymeric restraint may also contact a lower surface 183and/or side surface(s) of the capacitor element 120, either inconjunction with or in lieu of other surfaces.

Regardless of how it is applied, it is typically desired that thepolymeric restraint is also in contact with at least one surface of thehousing to help further mechanically stabilize the capacitor elementagainst possible delamination. For example, the restraint may be incontact with an interior surface of one or more sidewall(s), outer wall,lid, etc. In FIG. 1, for example, the polymeric restraint 197 is incontact with an interior surface 107 of sidewall 124 and an interiorsurface 109 of outer wall 123. While in contact with the housing, it isnevertheless desired that at least a portion of the cavity defined bythe housing remains unoccupied to allow for the inert gas to flowthrough the cavity and limit contact of the solid electrolyte withoxygen. For example, at least about 5% of the cavity volume typicallyremains unoccupied by the capacitor element and polymer restraint, andin some embodiments, from about 10% to about 50% of the cavity volume.

Once connected in the desired manner, the resulting package ishermetically sealed as described above. Referring again to FIG. 1, forinstance, the housing 122 may also include a lid 125 that is placed onan upper surface of side walls 124 after the capacitor element 120 andthe polymer restraint 197 are positioned within the housing 122. The lid125 may be formed from a ceramic, metal (e.g., iron, copper, nickel,cobalt, etc., as well as alloys thereof), plastic, and so forth. Ifdesired, a sealing member 187 may be disposed between the lid 125 andthe side walls 124 to help provide a good seal. In one embodiment, forexample, the sealing member may include a glass-to-metal seal, Kovar®ring (Goodfellow Camridge, Ltd.), etc. The height of the side walls 124is generally such that the lid 125 does not contact any surface of thecapacitor element 120 so that it is not contaminated. The polymericrestraint 197 may or may not contact the lid 125. When placed in thedesired position, the lid 125 is hermetically sealed to the sidewalls124 using known techniques, such as welding (e.g., resistance welding,laser welding, etc.), soldering, etc. Hermetic sealing generally occursin the presence of inert gases as described above so that the resultingassembly is substantially free of reactive gases, such as oxygen.

It should be understood that the embodiments described are onlyexemplary, and that various other configurations may be employed in thepresent invention for hermetically sealing a capacitor element within ahousing. Referring to FIG. 2, for instance, another embodiment of acapacitor assembly 200 is shown that employs a housing 222 that includesan outer wall 123 and a lid 225 between which a cavity 126 is formedthat includes the capacitor element 120 and polymeric restraint 197. Thelid 225 includes an outer wall 223 that is integral with at least onesidewall 224. In the illustrated embodiment, for example, two opposingsidewalls 224 are shown in cross-section. The outer walls 223 and 123both extend in a lateral direction (−y direction) and are generallyparallel with each other and to the lateral direction of the anode lead6. The sidewall 224 extends from the outer wall 223 in a longitudinaldirection that is generally perpendicular to the outer wall 123. Adistal end 500 of the lid 225 is defined by the outer wall 223 and aproximal end 501 is defined by a lip 253 of the sidewall 224.

The lip 253 extends from the sidewall 224 in the lateral direction,which may be generally parallel to the lateral direction of the outerwall 123. The angle between the sidewall 224 and the lip 253 may vary,but is typically from about 60° to about 120°, in some embodiments fromabout 70° to about 110°, and in some embodiments, from about 80° toabout 100° (e.g., about 90°). The lip 253 also defines a peripheral edge251, which may be generally perpendicular to the lateral direction inwhich the lip 253 and outer wall 123 extend. The peripheral edge 251 islocated beyond the outer periphery of the sidewall 224 and may begenerally coplanar with an edge 151 of the outer wall 123. The lip 253may be sealed to the outer wall 123 using any known technique, such aswelding (e.g., resistance or laser), soldering, glue, etc. For example,in the illustrated embodiment, a sealing member 287 is employed (e.g.,glass-to-metal seal, Kovar® ring, etc.) between the components tofacilitate their attachment. Regardless, the use of a lip describedabove can enable a more stable connection between the components andimprove the seal and mechanical stability of the capacitor assembly.

Still other possible housing configurations may be employed in thepresent invention. For example, FIG. 3 shows a capacitor assembly 300having a housing configuration similar to that of FIG. 2, except thatterminal pins 327 b and 329 b are employed as the external terminationsfor the anode and cathode, respectively. More particularly, the terminalpin 327 a extends through a trace 327 c formed in the outer wall 323 andis connected to the anode lead 6 using known techniques (e.g., welding).An additional section 327 a may be employed to secure the pin 327 b.Likewise, the terminal pin 329 b extends through a trace 329 c formed inthe outer wall 323 and is connected to the cathode via a conductiveadhesive 133 as described above.

The embodiments shown in FIGS. 1-3 are discussed herein in terms of onlya single capacitor element. It should also be understood, however, thatmultiple capacitor elements may also be hermetically sealed within ahousing. The multiple capacitor elements may be attached to the housingusing any of a variety of different techniques. Referring to FIG. 4, forexample one particular embodiment of a capacitor assembly 400 thatcontains two capacitor elements is shown and will now be described inmore detail. More particularly, the capacitor assembly 400 includes afirst capacitor element 420 a in electrical communication with a secondcapacitor element 420 b. In this embodiment, the capacitor elements arealigned so that their major surfaces are in a horizontal configuration.That is, a major surface of the capacitor element 420 a defined by itswidth (−x direction) and length (−y direction) is positioned adjacent toa corresponding major surface of the capacitor element 420 b. Thus, themajor surfaces are generally coplanar. Alternatively, the capacitorelements may be arranged so that their major surfaces are not coplanar,but perpendicular to each other in a certain direction, such as the −zdirection or the −x direction. Of course, the capacitor elements neednot extend in the same direction.

The capacitor elements 420 a and 420 b are positioned within a housing422 that contains an outer wall 423 and sidewalls 424 and 425 thattogether define a cavity 426. Although not shown, a lid may be employedthat covers the upper surfaces of the sidewalls 424 and 425 and sealsthe assembly 400 as described above. Optionally, a polymeric restraintmay also be employed to help limit the vibration of the capacitorelements. In FIG. 4, for example, separate polymer restraints 497 a and497 b are positioned adjacent to and in contact with the capacitorelements 420 a and 420 b, respectively. The polymer restraints 497 a and497 b may be positioned in a variety of different locations. Further,one of the restraints may be eliminated, or additional restraints may beemployed. In certain embodiments, for example, it may be desired toemploy a polymeric restraint between the capacitor elements to furtherimprove mechanical stability.

In addition to the capacitor elements, the capacitor assembly alsocontains an anode termination to which anode leads of respectivecapacitor elements are electrically connected and a cathode terminationto which the cathodes of respective capacitor elements are electricallyconnected. Referring again to FIG. 4, for example, the capacitorelements are shown connected in parallel to a common cathode termination429. In this particular embodiment, the cathode termination 429 isinitially provided in a plane that is generally parallel to the bottomsurface of the capacitor elements and may be in electrical contact withconductive traces (not shown). The capacitor assembly 400 also includesconnective members 427 and 527 that are connected to anode leads 407 aand 407 b, respectively, of the capacitor elements 420 a and 420 b. Moreparticularly, the connective member 427 contains an upstanding portion465 and a planar portion 463 that is in connection with an anodetermination (not shown). Likewise, the connective 527 contains anupstanding portion 565 and a planar portion 563 that is in connectionwith an anode termination (not shown). Of course, it should beunderstood that a wide variety of other types of connection mechanismsmay also be employed.

Regardless of its particular construction, the resulting capacitorassembly can exhibit a variety of beneficial properties. For example,the dissipation factor of the capacitor assembly may be maintained atrelatively low levels. The dissipation factor generally refers to lossesthat occur in the capacitor and is usually expressed as a percentage ofthe ideal capacitor performance. For example, the dissipation factor ofthe capacitor of the present invention is typically from about 1% toabout 25%, in some embodiments from about 3% to about 10%, and in someembodiments, from about 5% to about 15%, as determined at a frequency of120 Hz. The capacitor assembly may also be able to be employed in highvoltage applications, such as at rated voltages of about 35 volts ormore, in some embodiments about 50 volts or more, and in someembodiments, from about 60 volts to about 200 volts. The capacitorassembly may, for example, exhibit a relatively high “breakdown voltage”(voltage at which the capacitor fails), such as about 2 volts or more,in some embodiments about 5 volts or more, in some embodiments about 10volts or more, and in some embodiments, from about 10 to about 100volts. Likewise, the capacitor assembly may also be able to withstandrelatively high surge currents, which is also common in high voltageapplications. The peak surge current may be, for example, about 100 Ampsor more, in some embodiments about 200 Amps or more, and in someembodiments, and in some embodiments, from about 300 Amps to about 800Amps.

The present invention may be better understood by reference to thefollowing examples.

Test Procedures Equivalent Series Resistance (ESR)

Equivalence series resistance may be measured using a Keithley 3330Precision LCZ meter with Kelvin Leads 2.2 volt DC bias and a 0.5 voltpeak to peak sinusoidal signal. The operating frequency may 100 kHz andthe temperature may be 23° C.±2° C.

Dissipation Factor

The dissipation factor may be measured using a Keithley 3330 PrecisionLCZ meter with Kelvin Leads with 2.2 volt DC bias and a 0.5 volt peak topeak sinusoidal signal. The operating frequency may be 120 Hz and thetemperature may be 23° C.±2° C.

Capacitance

The capacitance may be measured using a Keithley 3330 Precision LCZmeter with Kelvin Leads with 2.2 volt DC bias and a 0.5 volt peak topeak sinusoidal signal. The operating frequency may be 120 Hz and thetemperature may be 23° C.±2° C. In some cases, the “wet-to-dry”capacitance can be determined. The “dry capacitance” refers to thecapacitance of the part before application of the solid electrolyte,graphite, and silver layers, while the “wet capacitance” refers to thecapacitance of the part after formation of the dielectric, measured in14% nitric acid in reference to 1 mF tantalum cathode with 10 volt DCbias and a 0.5 volt peak to peak sinusoidal signal after 30 seconds ofelectrolyte soaking.

Leakage Current

Leakage current may be measured using a leakage test meter at atemperature of 23° C.±2° C. and at the rated voltage (e.g., 16 volts)after a minimum of 60 seconds.

Humidity Testing

Humidity testing may conducted (25 parts) at a temperature of 85° C.,85% relative humidity, and at the rated voltage (e.g., 16 volts).Capacitance and ESR can be recorded after 120, 500, and 1,000 hours atrecovered samples and then compared to the initial measurement at 0hours. The recovery time after the test conditions may be from 6 to 24hours.

Example 1

70,000 μFV/g tantalum powder was used to form anode samples. Each anodesample was embedded with a tantalum wire, sintered at 1380° C., andpressed to a density of 5.8 g/cm³. The resulting pellets had a size of4.10×2.75×0.60 mm. The pellets were anodized to 42.0 volts inwater/phosphoric acid electrolyte with a conductivity of 8.6 mS at atemperature of 85° C. to form the dielectric layer. The pellets wereanodized again to 90 volts in a water/boric acid/disodium tetraboratewith a conductivity of 2.0 mS at a temperature of 30° C. for 25 secondsto form a thicker oxide layer built up on the outside. A conductivepolymer coating was then formed by dipping the anodes into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content 1.1% andviscosity 20 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 10 times.Thereafter, the parts were dipped into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content 2.0% andviscosity 20 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 3 times.Thereafter, the parts were dipped into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content of 2% andviscosity 160 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 8 times. Theparts were then dipped into a graphite dispersion and dried. Finally,the parts were dipped into a silver dispersion and dried. Multiple parts(1600) of 47 μF/16V capacitors were made in this manner and encapsulatedin a silica resin.

Example 2

Capacitors were formed in the manner described in Example 1, except thata different conductive polymer coating was used. The conductive polymercoating was formed by dipping the anodes into a solution ofpoly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2ylmethoxy)-1butane-sulphonicacid having a solids content of 1.9% (Clevios™ K, Heraeus). Uponcoating, the parts were dried at 125° C. for 20 minutes. This processwas not repeated. Thereafter, the parts were dipped into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content of 1.1% andviscosity 20 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 10 times.Thereafter, the parts were dipped into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content of 2.0% andviscosity 20 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 3 times.Thereafter, the parts were dipped into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content of 2% andviscosity 160 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 8 times. Theparts were then dipped into a graphite dispersion and dried. Finally,the parts were dipped into a silver dispersion and dried. Multiple parts(800) of 47 μF/16V capacitors and encapsulated in a silica resin.

Example 3

Capacitors were formed in the manner described in Example 1, except thata different conductive polymer coating was used. The conductive polymercoating was formed by dipping the anodes into a solution ofpoly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butane-sulphonicacid having a solids content of 1.9% (Clevios™ K, Heraeus), Uponcoating, the parts were dried at 125° C. for 20 minutes. This processwas repeated 10 times. Thereafter, the parts were dipped into adispersed poly(3,4-ethylenedioxythiophene) having a solids content of2.0% and viscosity 20 mPa·s (Clevios™ K, Heraeus). Upon coating, theparts were dried at 125° C. for 20 minutes. This process was repeated 3times. Thereafter, the parts were dipped into a dispersedpoly(3,4-ethylenedioxythiophene) having a solids content of 2% andviscosity 160 mPa·s (Clevios™ K, Heraeus). Upon coating, the parts weredried at 125° C. for 20 minutes. This process was repeated 8 times. Theparts were then dipped into a graphite dispersion and dried. Finally,the parts were dipped into a silver dispersion and dried. Multiple parts(800) of 47 μF/16V capacitors and encapsulated in a silica resin.

The finished capacitors of Examples were then tested for electricalperformance. The median results of capacitance, DryNVet capacitance, Df,ESR and are set forth below in Table 1. The wet capacitance was 48.97μF.

TABLE 1 Electrical Properties Initial Wet-to-Dry Initial Initial InitialCap Cap Df ESR DCL [μF] [%] [%] [mohms] [μA] Example 1 35.38 72.25 1.954.1 4.83 Example 2 41.19 84.11 1.9 46.7 2.25 Example 3 41.37 84.49 2.065.5 5.43

The finished capacitors of Examples were the tested at 85° C., 85%relative humidity, and at the rated voltage. Capacitance and ESR wererecorded at 0, 120, 500, and 1,000 hours. The results are set forthbelow in Table 2.

TABLE 2 Humidity Testing (85° C., 85% Relative Humidity) Time Cap ESR[hrs] [μF] [mohms] Example 1 0 34.85 53.4 120 46.63 102.7 500 46.06517.4 1000 39.20 1455.5 Example 2 0 41.00 46.8 120 47.18 49.9 500 47.0653.9 1000 47.05 60.1 Example 3 0 41.34 69.2 120 47.57 74.9 500 47.5286.0 1000 47.50 91.7

These and other modifications and variations of the present inventionmay be practiced by those of ordinary skill in the art, withoutdeparting from the spirit and scope of the present invention. Inaddition, it should be understood that aspects of the variousembodiments may be interchanged both in whole or in part. Furthermore,those of ordinary skill in the art will appreciate that the foregoingdescription is by way of example only, and is not intended to limit theinvention so further described in such appended claims.

What is claimed is:
 1. A capacitor assembly that is in contact with anatmosphere having a relative humidity of about 40% or more, thecapacitor assembly comprising a capacitor element that includes an anodethat contains a dielectric formed on a sintered porous body and a solidelectrolyte overlying the anode, wherein the solid electrolyte includesan intrinsically conductive polymer containing repeating units havingthe following formula (I):

wherein, R is (CH₂)_(a)—O—(CH₂)_(b); a is from 0 to 10; b is from 1 to18; Z is an anion; and X is a cation.
 2. The capacitor assembly of claim1, wherein the capacitor assembly exhibits an ESR value of less thanabout 200 mohms, as determined at an operating frequency of 100 kHz. 3.The capacitor assembly of claim 2, wherein the capacitor assemblyexhibits an ESR value of less than about 200 mohms after being exposedto the atmosphere for 1000 hours at a temperature of about 85° C.
 4. Thecapacitor assembly of claim 1, wherein the capacitor assembly exhibits acapacitance value of about 30 nanoFarads per square centimeter or more,as determined at a frequency of 120 Hz.
 5. The capacitor assembly ofclaim 4, wherein the capacitor assembly exhibits a capacitance value ofabout 30 nanoFarads per square centimeter or more after 1000 hours at atemperature of about 85° C.
 6. The capacitor assembly of claim 1,wherein the anode body includes tantalum.
 7. The capacitor assembly ofclaim 1, wherein a is 1 and b is 3 or
 4. 8. The capacitor assembly ofclaim 1, wherein Z is SO₃.
 9. The capacitor assembly of claim 1, whereinX is an alkali metal.
 10. The capacitor assembly of claim 1, wherein thepolymer ispoly(4-(2,3-dihydrothieno-[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butane-sulphonicacid, salt),poly(4-(2,3-dihydrothieno-[3,4-b][I,4]dioxin-2-ylmethoxy)-I-propanesulphonicacid, salt), or a combination thereof.
 11. The capacitor assembly ofclaim 1, wherein the solid electrolyte contains one or more innerlayers, wherein the inner layers contain the intrinsically conductivepolymer.
 12. The capacitor assembly of claim 11, wherein the solidelectrolyte contains from 5 to 15 inner layers.
 13. The capacitorassembly of claim 11, wherein the inner layers are generally free ofextrinsically conductive polymers.
 14. The capacitor assembly of claim11, wherein the solid electrolyte contains one or more outer layers,wherein at least one of the outer layers is formed from a dispersion ofparticles that contain a polymeric counterion and an extrinsicallyconductive polymer having repeating units of the following formula(III):

wherein, R₇ is a linear or branched, C₁ to C₁₈ alkyl radical; C₅ to C₁₂cycloalkyl radical; C₆ to C₁₄ aryl radical; C₇ to C₁₈ aralkyl radical;or C₁ to C₄ hydroxyalkyl radical, or hydroxyl radical; and q is aninteger from 0 to
 8. 15. The capacitor assembly of claim 14, wherein atleast one of the outer layers contains a hydroxyl-functional nonionicpolymer.
 16. The capacitor assembly of claim 1, further comprising ahousing within which the capacitor element is enclosed.
 17. Thecapacitor assembly of claim 16, wherein the housing is formed from aresinous material that encapsulates the capacitor element.
 18. Thecapacitor assembly of claim 16, wherein the housing defines an interiorcavity within which the capacitor element is positioned, wherein theinterior cavity has a gaseous atmosphere that has a relative humidity ofabout 40% or more.
 19. The capacitor assembly of claim 18, wherein thegaseous atmosphere contains an inert gas.
 20. A method comprisingexposing a capacitor assembly to an atmosphere having a relativehumidity of about 40% or more, the capacitor assembly comprising acapacitor element that includes an anode that contains a dielectricformed on a sintered porous body and a solid electrolyte overlying theanode, wherein the solid electrolyte includes an intrinsicallyconductive polymer containing repeating units having the followingformula (I):

wherein, R is (CH₂)_(a)—O—(CH₂)_(b); a is from 0 to 10; b is from 1 to18; Z is an anion; and X is a cation.